Influence of anionic and cationic reverse micelles on nucleophilic aromatic substitution reaction between 1-fluoro-2,4-dinitrobenzene and piperidine

Abstract

The nucleophilic aromatic substitution (S(N)Ar) reaction between 1-fluoro-2,4-dinitrobenzene and piperidine (PIP) were studied in two different reverse micellar interfaces: benzene/sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (AOT)/water and benzene/benzyl-n-hexadecyl dimethylammonium chloride (BHDC)/water reverse micellar media. The kinetic profiles of the reactions were investigated as a function of variables such as surfactant and amine concentration and the amount of water dispersed in the reverse micelles, W0 = [H2O]/[surfactant]. In the AOT system at W0 = 0, no micellar effect was observed and the reaction takes place almost entirely in the benzene pseudophase, at every AOT and PIP concentration. At W0 = 10, a slight increment of the reaction rate was observed at low [PIP] with AOT concentration, probably due to the increase of micropolarity of the medium. However, at [PIP] > or = 0.07 M the reaction rates are always higher in pure benzene than in the micellar medium because the catalytic effect of the amine predominates in the organic solvent. In the BHDC system the reaction is faster in the micellar medium than in the pure solvent. Increasing the BHDC concentration accelerates the overall reaction, and the saturation of the micellar interface is never reached. In addition, the reaction is not base-catalyzed in this micellar medium. Thus, despite the partition of the reactants in both pseudophases the reactions effectively take place at the interface of the aggregates. The kinetic behavior can be quantitatively explained taking into account the distribution of the substrate and the nucleophile between the bulk solvent and the micelle interface. The results were used to evaluate the amine distribution constant between the micellar pseudophase and organic solvent and the second-order rate coefficient of S(N)Ar reaction in the interface. A mechanism to rationalize the kinetic results in both interfaces is proposed.